JPS59157972A - Sodium-sulfur battery aggregate - Google Patents

Abstract

PURPOSE:To improve heat retaining efficiency and increase anticorrosion and safety by densely arranging a cylindrical type Na-S single cell in a polygonal container. CONSTITUTION:A number of cylindrical type Na-S single cells C are densely arranged in a hexagonal shape and their outside is entirely sealed by a fixed frame consisting of inside and outside double containers 23 and 24. The inside container 23 is provided with heater terminals 25 and 26 on upper and lower ends and a sheathing type electrical heater 27 is wound round the external surface of the inside container 23, as shown in Fig. 6 Internal inactive gas 22 can be heated by applying current through the heater terminals 25 and 26. Since this battery aggregate is of a hexagonal dense array type and the section between the inside and outside double containers 23 and 24 is filled with a heat insulator 21, the heat capacity leaked externally is low and heat retaining property is good. In addition, the inside container 27 filled with the inactive gas 22 prevents the corrosion of the single cells from advancing up to the high operating temperature.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a sodium-sulfur battery (hereinafter referred to as N-sulfur battery) which is a secondary battery.
a-8ljLm),
In particular, the dense arrangement of cylindrical Na-8 cells, improved heat retention efficiency, and increased edibility and safety of Na-
Regarding a 3-battery assembly.

[Prior art]

A conventional example of a single Na-3 battery (hereinafter referred to as a single battery) will be explained with reference to a side view shown in FIG. N indicated entirely by C
The a-8 unit cell is a cylindrical type, and a solid electrolyte 8 with a bottom is used for melting and sulfurization as a first-field active material.
This is achieved through ion conduction due to a chemical reaction between the ionized sodium oxide and dissolved sodium 13 as the cathode active material. In order to retain molten sulfur 1O and obtain electronic conductivity, sulfur 10 was impregnated into the graphite fiber 9 having voids. Further, stainless steel fibers 14 are inserted inside the solid electrolyte 8 in order to prevent the stain pond from being damaged due to the reaction between the molten sulfur lO and the molten sodium 13 when the solid electrolyte 8 cracks. Since molten sulfur and molten sodium are both highly corrosive substances, the anode container 3, cathode container 4, anode cap 2, cathode character f5, anode tube 1, and cathode tube 6 are each 1?
Yushokuboichi treatment has been applied. The operating temperature of the Na-8'' pond must be below 350°C, and at this temperature molten sulfur 10 and molten sodium 13 undergo a chemical reaction.
2Sx is liquid and corrosive.

The 21st image is a plan view showing a conventional example of an Na-8 battery assembly formed by aggregating a large number of such Na-8 cell batteries, in which a large number of cylindrical Na-8 cells C are arranged in an array. A fixing frame 16 with open upper and lower surfaces is provided on the outer periphery of the fixing frame 16 to fix the cell C.

FIG. 3 is a side cross-sectional view taken along the line A--A in FIG. Electrodes 17. are placed above and below the cell group.
20 is connected to constitute a charging/discharging terminal of the battery. N
Since the A-8 battery needs to be maintained at an operating temperature of 3000 to 350C, a high-temperature insulating gas such as nitrogen or air is flowed through the upper and lower openings of the fixed frame 16 as shown by the arrows in FIG.

The conventional Na-8 battery assembly as described above has the following drawbacks.

(1) Since it is necessary to circulate heat insulating gas in the space between the cylindrical cells, the cells cannot be densely arranged.

(2) Separate equipment is required to heat the insulated gas and to blow air.

(3) In the event that a single cell is damaged and a large amount of heat is generated due to the Na-8 reaction, break the battery assembly by 1 sL.
The effect also spreads to surrounding battery assemblies.

[Purpose of the invention]

The purpose of the present invention is to increase the density of high-temperature Na-3 single cells, improve heat insulation efficiency, eliminate separate heat insulation equipment, improve corrosion resistance of single cells at high temperatures, and improve the Na-3 reaction that occurs when batteries are damaged. It is an object of the present invention to provide an Na-8 battery assembly which eliminates the conventional drawbacks by making it possible to avoid the influence of heat generation on the surroundings.

[Summary of the Invention] ・“The Na-8 battery assembly according to the present invention, in the first invention, consists of cylindrical Na-8 cells arranged close to each other in a polygonal shape.
A fixed frame consisting of an inner and outer double container in the shape of a lJr surface polygon that accommodates the cell group and seals the entire 1 m of the cell group, and the space between the inner and outer double containers is filled. 'Ff9' is composed of a heat insulating material and an inert gas filled in the inner container of the double container, and an electric heater is disposed on the outer circumferential surface of the inner container. In the second invention, Na-9 of the first invention
Each Na-8 cell in the battery assembly houses a solid electrolyte in the shape of a circular box with a bottom, and molten thorium as a cathode active material and molten sulfur as an anode active material placed between the solid electrolyte. It has a cylindrical metal container constructed by welding an end face f to a metal circular pipe that has been subjected to corrosion prevention treatment, and graphite fibers that are not impregnated with sulfur are placed inside the welded part of the anode side cap of the container. It is characterized by being made of an Na-8 cell with a spacer inserted therein.

[Embodiments of the invention]

FIG. 4 is a plan cross-sectional view showing an embodiment of the Na-8 Seike aggregate of the present invention, in which a large number of cylindrical Na-8 cells C are densely arranged in a hexagonal shape, and the outside is double-walled. container 23.24
Completely sealed with a fixed frame consisting of

The space inside the inner container 23 is filled with an inert gas 22 such as argon or nitrogen. Inner container 23 and outer 1tl
All the spaces between the llg units 24 are filled with heat insulating insulation 21.

FIG. 5 is a side view of the branch of FIG. 4. Heater terminals 25 and 26 are provided at the upper and lower ends of the inner container 23, respectively, and a sheath type blood heater 27 is wound around the outer peripheral surface of the inner container 23 as shown in FIG. .26
By passing through the gas, the inert gas 22 inside is heated and quenched.

Battery terminal 28. 29 is a terminal for charging and discharging the battery C, and also serves as a spacer for identifying the IkC to the inner container 23. The hermetic seal 30 serves to insulate the battery terminals 28, 29 and the inner container 23.

This battery assembly is of a hexagonal dense arrangement type, and the inner and outer double containers 23 and 24 are filled with heat insulating material 21, so the amount of heat leaked to the outside is small and heat retention is good. The inert gas 22 filled in the inner container 23 prevents corrosion of the cells at high operating temperatures.
1 insulates the heat of dog 1, ;・ that occurs when the battery is damaged,
It also has the effect of preventing the surrounding battery east combinations from being affected.

In the above embodiment, the single cells C are arranged in a single stage in the axial direction (L1(i') as shown in FIG. 5, but it is also possible to arrange them in multiple stages in the axial direction. It should be noted that the arrangement of the ponds does not necessarily have to be hexagonal; it can be arranged squarely, as in the conventional example shown in Figure 2, but in order to reduce the heat dissipation area and increase density. A hexagonal or hexagonal arrangement is preferred.

Next, the structure of an improved Na-8 cell suitable for use in the Na-8 battery assembly according to the present invention will be described.

As mentioned earlier in the explanation of Figure 1, Na-3 [
At the operating temperature of the pond, molten sulfur 10- and molten sodium 13 chemically react to form Na2Sx, which is a corrosive liquid. Therefore, it is impossible to completely preserve the liquid Na2Sx in the graphite fiber 9, which is the material to be impregnated, and for this reason, the welded part 12 between the anode container 3 and the positive/feed cap is easily corroded by Na25X. , further welding part 12
Corrosion spreads to the anode container 3, and the life of the Na-8 cell is shortened.
This may cause performance deterioration or damage. Also, the welded part 12 at the end
The space 11 inside the sulfur impregnated graphite fiber 9 deteriorates the positioning accuracy of the sulfur-impregnated graphite fiber 9, which adversely affects the uniformity of the performance of the Na-8 cell.

Therefore, in the Na-8 battery assembly of the second invention, in order to eliminate the drawbacks of the conventional example, 11 (spaces u) of the anode side end welding locations are not impregnated with sulfur and sulfur. Improved Na-8 with spacer like graphite fiber
It uses single batteries.

An example of such an improved Na-8 cell is shown in FIG. In this figure, the same parts as those in FIG. 1 are represented by the same reference numerals. This improved battery has a structure in which a space 15 made of accumulated lead fibers which is not impregnated with corrosion 1 is housed in the space 11 in FIG. 1 as shown in FIG. 7. To this J: ,! l) % (1/Improvement of battery life, (2) '7ti', equalization of pond performance. Liquid Na2S
x flows into the welded part 12 due to the existence of the end beam gap 11 inside the welded part 12 and corrodes it, whereas in the improved Na-8 battery of the second invention, from the graphite fiber 15 shown above, This causes the Na 2 S x to be held in the waveform 15, which leads to corrosion of the welded part 12! The above effect (1) can be obtained by reducing the amount of water. Further, the effect (2) is based on the improvement in the accuracy of positioning the graphite fiber 9 impregnated with the sulfuric acid 10. This is not true
-8 This is of great significance in terms of battery characteristics. That is, Na-
Since the 8 battery is formed by ionic conduction through the solid electrolyte 8, graphite fibers 9 impregnated with sulfur modified 10 are used.
If the position of
By providing a layer of graphite fibers as described above, it is possible to equalize the performance of each cell.

〔Effect of the invention〕

According to the present invention, it is omitted to flow heat insulating gas between the internal cells of the Na-8'1llll pond assembly.
7JG of 1 gas Not only is there no need for separate equipment for heat and supply, but it is also possible to arrange the cells in a dense arrangement. Since it is sealed, a heat insulating material is filled between the double containers, and an inert gas is filled in the inner container containing the battery details.
Many effects can be obtained, such as improved heat retention, prevention of corrosion of the internal cells, prevention of negative effects on the surroundings by blocking large amounts of heat generated when the cells are damaged, and therefore improved safety. However, in the Na-8-1 electrolyte combination of the second invention, the corrosion resistance and uniformity of performance of the individual cells constituting the cell group are improved.In particular, these cells are bad for Japanese roof tiles. The performance of the battery group can be improved without affecting each other.

[Brief explanation of the drawing]

Figure 1 is a plan view of the branch of the conventional Na-8 single cell pond, Figure 2 is a plan view of the conventional Na-8 cell combination, and Figure 3 is the 2nd (8) plate.
4 is a plan sectional view of an embodiment of the Na-8 cell assembly of the present invention, FIG. 5 is a branch diagram of the battery assembly of FIG. 4, and FIG. FIG. 7 is an external view of the inner full container in the example, and FIG. 7 is a side view of the Na-8 single electric current used to combine the Na-5 electric current of the present invention. ■...Anode tube 2...i@polar medium cap 3...Anode container 4...Cathode container 5...Nath;
Box carrier, f 6... Cathode tube 8... IAjA1 constitutional decomposition 9... Sulfur-impregnated graphite fiber 10... Molten sulfur 11... Space 12... Welding part
l 3... Molten sodium 4... Stainless steel fiber 15... Spacer made of sulfur-non-impregnated graphite fiber, 16
...Fixed frame 17...Electrode 18...Insulator 19...Scale-sa 20...Electrode
21...Insulating material 22...Inert material
23...Inner container 24...Outer container 25.
26...Flash terminal 27...Heater 28.29...Battery terminal 30...Hermetic seal multi-knee 1 Figure 2 Figure 3

Claims (1)

[Scope of Claims] 1. A group of cylindrical Na-8 cells arranged in close proximity to q in a polygonal shape, and an inner and outer double cell with a polygonal cross-section that accommodates the group of cells and completely seals the periphery 9 thereof. A container, a heat insulating material filled between the inner and outer double containers, an inert gas filled in the inner and outer containers of the double containers, and the outer periphery of the inner container. A sodium-sulfur battery assembly characterized in that a 'r6 air heater is installed on its surface. 2. A cylindrical solid electrolyte with a bottom, and a metal circle treated to prevent corrosion and containing molten sodium as a cathode active material and molten sulfur as a candle active material placed between the solid electrolyte. It has a cylindrical metal container constructed by welding an end cap 7f to a piezo, and a slot made of graphite fiber that is not impregnated with sulfur is inserted into one welding point of the anode side cap of the container. A cell group in which a large number of Na-8 cells are arranged close to each other in a polygonal shape, and an inner and outer double cell with a polygonal cross section that accommodates this cell group and completely seals its periphery. 9, an outer circumferential surface of the inner container, consisting of a container, an insulated side filled between the double containers, and an inert gas filled in the inner container of the double containers. A sodium-sulfur battery assembly characterized in that an electric heater is provided in the battery.